JPS609968A - Fiber treating agent - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a treatment agent for fibers that does not cause yarn breakage, coloring, tarring or fuming during use.

A series of processes for melt-spinning thermoplastic synthetic polymers such as polyethylene terephthalate, polycaproamide, and polyhexamethylene adipamide into fibers includes a step of applying an oil agent to the fiber surface.

Conventionally, various oils have been proposed for use in this process, but when these known oil compositions are applied to the surface of the curved fibers, the heat stretching and heat treatment steps that follow the oil application process can be completed. There are problems in that thread breakage occurs and the oil composition evaporates or decomposes, producing so-called smoke.

In particular, fibers made of polyethylene terephthalate, polycapramide, polyhexamethylene adipamide, etc. are prone to yarn breakage and smoke generation during the fiber manufacturing process where they are hot-drawn at high temperatures. This not only reduces operability but also increases the amount of waste, leading to problems such as a considerable increase in manufacturing costs.

In recent years, in the production of industrial synthetic fibers, there has been a strong demand for high-strength yarns, and in order to stably produce high-strength yarns, it is strongly desired to reduce the number of yarn breakages.

Furthermore, when smoke is generated during the manufacturing process, it not only pollutes the air in the process and worsens the working environment, causing abnormalities to the throats and eyes of workers, but also causes the contaminated air to leak outside the factory. Don't come out and cause trouble to the surrounding residents.
Close-up of environmental problems 1 As the environmental problems become more severe, there is a strong demand for technology to prevent smoke generation more than ever before.

Under these circumstances, in recent years, many oil compositions have been studied that reduce the occurrence of yarn breakage and do not emit smoke, and although they have shown considerable effectiveness, there is still no way to stabilize high-strength yarn without deteriorating the working environment. It is difficult to manufacture, and when the obtained fiber is used as a rubber reinforcing material, one cannot expect much from the adhesion between the fiber and rubber.

For example, JP-A-52-103594 discloses a treatment agent for fibers with excellent heat resistance, in which a dicarboxylic acid such as thiodicarboxylic acid is reacted with a polyhydric alcohol and its alkylene oxide adduct, and carboxyl groups are added at both ends. A fiber treatment agent containing a compound obtained by further esterifying a low molecular weight polyester with a monohydric alcohol has been proposed, but this treatment agent has superior heat resistance compared to other treatment agents. However, it is not possible to completely avoid discoloration, cooling, and smoke generation during use, and problems still remain.

Therefore, the present inventors conducted intensive studies with the aim of obtaining a fiber treatment agent that does not cause yarn breakage, coloring, tarring, or smoke during use, and found that a specific emulsifier was combined with the above compounds in a specific blending ratio. By applying it to thermoplastic synthetic fibers, it is possible to completely prevent fiber breakage, tarring, and smoke generation even when the fibers are heated by heating stretching or heat treatment, and it also improves the smoothness of the fibers and the adhesion to rubber. It has been discovered that a treatment agent for fibers that does not cause deterioration can be obtained, and the present invention has been achieved.

That is, the present invention has (Al general formula RO[0CXC00YQ
] n0CxCO2 [However, RO in the formula has 6 to 30 carbon atoms
The monohydric alcohol residue of -ocxao- is -0OA,
SA2 Co-1-OCAa OA4 CiOH and -0CA6CO- (where A1, A2, A3 and A
4 is an alkylene group having 1 to 6 carbon atoms, S is a sulfur atom,
A6 represents an alkylene group having 1 to 8 carbon atoms]; -0YO- represents a polyhydric alcohol residue; Z is 10I (or -
At least one compound represented by 〇B' (where -OR' represents a monohydric alcohol residue having 1 to 3 carbon atoms, and n represents an integer of 1 to 6) and [Bl (al
at least one emulsifier selected from higher fatty acids, polyhydric alcohols, and expanded products of polyethylene oxide and/or polypropylene oxide; and (b) castor oil or ethylene oxide and/or propylene oxide adducts of hydrogenated castor oil. , France)/fB
(7) A fiber processing agent is provided in which the ratio is 40.80 parts by weight/60 to 20 parts by weight (total 100 parts by weight).

The main component of the fiber treatment agent of the present invention (Al general formula RO
The compound represented by (ocxcooyo]n0cXcOZ (hereinafter abbreviated as a smoothing agent compound) is, for example, (a)
tediocarboxylic acid of the formula f(QQQA, SA2 C0OH, oxydicarboxylic acid of the formula HOO(jA30A4 C0OH and HOOOA, 0OOH
At least one of the aliphatic dicarboxylic acids represented by (b) a polyhydric alcohol represented by the formula HOYOH, an alkylene oxide adduct S of a polyhydric alcohol, an alkylene oxide adduct S of a polyhydric phenol, or a partial ester thereof obtained by widening with seeds to obtain a low molecular weight polyester having carboxyl groups at both ends, and then esterifying the carboxyl groups with a monohydric alcohol of formula ROH or R'OH (mono- or diesterification) It is a compound.

Therefore, in the +Al smoothing agent compound represented by the above general formula, monohydric alcohols having 6 to 30 carbon atoms forming the monohydric alcohol residue represented by RO include octyl alcohol, 2-ethylhexyl alcohol, lauryl alcohol, cetyl alcohol, Aliphatic saturated alcohols with straight or side chains such as stearyl alcohol, instearyl alcohol and synthetic alcohols, aliphatic unsaturated alcohols such as allyl alcohol, crotyl alcohol and oleyl alcohol, matcha alcohol,
It includes aliphatic saturated and unsaturated alcohols such as base alcohols and coconut cyclic base alcohols, aliphatic alcohols such as cyclopentanol and cyclohexanol, and aromatic alcohols such as benzyl alcohol and cinnamyl alcohol, but But aliphatic monohydric alcohol cheeks are preferred. Furthermore, as the monohydric alcohol having 1 to 30 carbon atoms forming the monohydric alcohol residue represented by R'O in Z in the above formula, in addition to those represented by RO above, methyl alcohol, ethyl alcohol, propyl alcohol, Examples include n-propyl alcohol, isobutyl alcohol, and t-butyl algol. Here, the carbon number of RO is preferably 6 to 30, especially 10 to 18, and the carbon number of R'O is preferably 1 to 50, especially 6 to 50. If each carbon number exceeds 30, tar formation occurs. Also, when the number of carbon atoms in R'O is 6,
If it is less than this, it is not preferable because it tends to generate smoke.

In addition, in the general formula of the smoothing agent compound (A) above, -0C
XCO- is -〇0AISA2 Go-5-0CAs O
A4 Co- and -0CAs C0- (where Al
, A2, A3 and A4 represent an alkylene group having 1 to 6 carbon atoms, S represents a sulfur atom, and A6 represents an alkylene group having 1 to 8 carbon atoms. ) is a dicarboxylic acid residue selected from
Dicarboxylic acids that form these residues include thiodicarboxylic acids such as thiodiacetic acid and thiodipropionic acid, oxydicarboxylic acids such as oxydiacetic acid and oxydipropionic acid, and succinic acid, adipic acid, azelaic acid 3, and sepacic acid. Examples include aliphatic dicarboxylic acids,
Among these, thiodicarboxylic acid is preferred.

Furthermore, in the general formula of the above (Al smoothing agent compound)
O- is a divalent group selected from a polyhydric alcohol residue, an alkylene oxide adduct residue of a polyhydric alcohol, and an alkylene oxide adduct residue of a polyhydric phenol; Ethylene glycol, propison glycol, trimethylene glycol, 1゜4-butanediol, 1,6-hexanediol, diethylene glycol and neopentyl glycol, general bisphenol A1 bisphenol P1 bisphenol B and bisphenol S Bisphenols such as dioxydiethyl ether and dioxydipropyl ether, diols such as 1,4-butanediol, glycerin, diglycerin, polyglycerin, trimethylolethane, pentaerysphtol, sorbitol, and Examples include polyols such as trimethylolethane or partial esters thereof (having at least two hydroxyl groups), and alkylene oxide adducts of polyhydric alcohols include alkylene oxides (ethylene oxide, propylene oxide, etc.) to the polyhydric alcohols. and butylene oxide, etc.) or their partial esters (provided that they have at least two hydroxyl groups); alkylene oxide adducts of polyhydric phenols include catechol, resorcinol, hydroquinone,
Polyhydric phenols such as pyrogallol and phloroglycine. Similar to the above, compounds with alkylene oxide added or partial esters thereof (however, at least 2
hydroxyl groups). Examples of alkylene oxide adducts of bisphenols include compounds to which alkylene oxide is added, similar to the above for bisphenol A and bisphenol St. The number of moles of these alkylene oxides added is usually 1
~30 mol is suitable. Among the above compounds, glycols.

Particularly preferred is neopentyl glycol.

The most preferred fA) smoothing agent compound, which is the main component of the fiber treatment agent of the present invention, is the following compound, which has a HisO+50
0(i(CF!2J2S(OH2)2C00CH2G0
1%0OC(Ocho ■2in2E3ccFi2)lCOOC
1aH3s Section Correction 3 The above (Al smoothing compound) can be used alone as a treatment agent for fibers, but when used alone, it is impossible to avoid taring and fuming during fiber stretching and heat setting. However, the fiber treatment agent of the present invention has the above f.
Along with the Al smoothing compound, certain emulsifier components, specifically fB) (tripartite reaction products of Al higher fatty acids, polyhydric alcohols and polyethylene oxide and/or polypropylene oxide and fB) castor oil or hydrogenated castor It is characterized by the combination of at least one selected from the group consisting of ethylene oxide and/or propylene oxide in oil, thereby completely eliminating thread breakage, tarring and fuming during use.

Here, the higher fatty acids in one compound (a) of the emulsifier component (B) include, for example, lauric acid, valmitic acid, stearic acid, and cerotic acid having 12 to 2 carbon atoms.
6 saturated fatty acids, unsaturated fatty acids having 18 to 22 carbon atoms, such as oleic acid, elaidic acid, linoleic acid and lylunic acid, and saturated aliphatic dicarboxylic acids, such as dodecanoic acid and octadecanoic acid.

The polyhydric alcohol is preferably trivalent or higher glycerin, monoalkylglycerin, 1.2.3-butanetriol, 1.2.3-pentanetriol, dialkyl-substituted glycerin, trialkyl-substituted glycerin, elidrift, pentaelylglycerin. Drift, attonite, xylitol, sorbitol, mannitol, etc. are used.

Among polyethylene oxide and/or polypropylene oxide, polyethylene oxide is preferably used, but polypyrene oxide may be used alone or in combination, and these usually have 5 to 60 repeating units, preferably 5 to 60 repeating units. 10 to 45 are used.

A reaction product (compound (b)) consisting of these higher fatty acids, polyhydric alcohol, polyethylene oxide and/or polypropylene oxide (polyalkylene oxide)
) can be obtained by first making a condensate of a polyhydric alcohol and a polyalkylene oxide, and then reacting this condensate with a higher fatty acid to form an ester or partial ester. Examples include methods such as making a partial ester of and condensing it with an alkylene oxide or subjecting it to an esterification reaction, and either compound (b) is a compound in which a higher fatty acid, a polyhydric alpure, and a polyalkylene oxide are bonded together. It is.

Furthermore, conventionally known castor oil or hydrogenated castor oil is used in the compound fbl of FB+emulsifier component, and the number of moles of ethylene oxide and/or propylene oxide added thereto is 5 to 60 moles, preferably 10 to 45 moles. It is.

In the present invention, it is particularly preferred to use as the Bl emulsifier component an ethylene oxide adduct of hydrogenated castor oil and an ethylene oxide adduct of ruby/triolate.

In addition, in the fiber treatment agent of the present invention, the intended purpose can only be achieved by combining the above-mentioned (Al smoothing agent compound with the above-mentioned specific (B) emulsifier compound, and other than the above-mentioned fE). Commonly known emulsifiers such as higher alcohol ethylene oxide adducts, esters of polyethylene glycol and higher fatty acids, etc.
Even if used in combination with other ingredients, tarring and smoke generation during use cannot be improved.

The fiber treatment agent of the present invention includes the above-mentioned [Al smoothing agent compound and (B
l emulsifier compound +Al/(E) weight ratio is 40~
80 copies/60~20 copies, 1 special 50~70 copies 150~
Included in a proportion of 30 copies (total 100 copies). If the ratio of FB+emulsifier compound is less than 20 parts, the emulsified state often becomes unstable, which is not preferable. Moreover, if it exceeds 60 parts, frictional force increases and thread breakage occurs frequently during spinning, which is not preferable.

The fiber treatment agent of the present invention contains the above compounds FA) and f
A more preferable effect is exhibited when (C) an ethylene oxide and/or propylene oxide adduct of an alkylamine is further contained in addition to B).

The alkylamine mentioned here has 2 to 30 elementary atoms.
primary and secondary amines, preferably lauryl, cetyl and stearylamine. The number of moles of ethylene oxide and/or propylene oxide added is preferably 5 to 30, more preferably 10 to 20.

In this case, the weight ratio of the compound fAl/FBl/fat is 40-80 parts, 15-59 parts/1-15 parts, etc.
40-70 copies/30-80 copies/2-10 copies (total 10 copies)
A proportion of 0 parts) is preferred.

Note that the fiber treatment agent of the present invention contains the above-mentioned compounds fAl, fBt.
In addition to fcl, a third component such as an antistatic agent, a viscosity reducing agent such as mineral oil, and an adhesion improver to rubber such as a polyepoxy compound may be further contained.

The fibers to be treated with the fiber and miscellaneous treatment agent of the present invention are thermoplastic synthetic fibers such as polyethylene terephthalate, polyhexamethylene adipamide, and polycaproamide, but are particularly suitable for heating bodies of 170°C or higher, or The target fibers are those obtained through a process of spinning using a heated atmosphere.

The treatment with the fiber treatment agent of the present invention means an operation in which the fibers are brought into contact with the treatment agent composition. Therefore, in the present invention, the fiber treatment agent can be applied to synthetic fibers at any stage after spinning, such as during or after drawing, by immersing the yarn in the fiber treatment agent in the form of a water-containing oil such as a water emulsion. Alternatively, this can be done by applying a fiber treatment agent to the yarn using a roller or the like. In particular, it is preferable to apply a fiber treatment agent to the undrawn yarn before drawing in order to improve drawability and prevent smoke generation during drawing.

When synthetic fibers are produced by applying the fiber treatment agent of the present invention, yarn breakage during heating and drawing is reduced, making it possible to stably manufacture high-strength yarns, and preventing tarring of the fiber treatment agent due to heat treatment. It has an excellent effect in that it can sufficiently improve problems associated with smoke generation such as vaporization.

Moreover, if smoke generation is prevented by the present invention, there will be no contamination of the heating element during production, and the emulsion stability of the fiber treatment agent will be good, and this can be done without causing any disadvantages in other respects.

The present invention will be explained below using examples.

Examples 1 to 6, Comparative Examples 1 to 4 1500 denier, 288 filament polyethylene terephthalate filament yarn was spun in a conventional manner,
A 15% water emulsion type fiber treatment agent having the composition shown in Table 1 was applied using a roller, and then stretched at 230° C. using a hot roller and a hot plate at a stretching rate of 57 times. The amount of fiber treatment agent attached to the fibers was 1.0%.

The smoking properties of the hot roller and hot plate during stretching, the dirtiness of the hot roller and hot plate, the stretching property (number of thread breaks during stretching), and the emulsification stability of the fiber treatment agent were measured according to the following criteria, and the results are shown in the table below. -1f was shown.

Smoking property: Smoking was observed with the naked eye on hot rollers and hot plates during stretching, and evaluated using the following criteria.

◎: No smoke ○: 〃 Not at all △: 〃 Lots of dirt on the hot roller and hot plate: There is a lot of dirt, and the number of thread breakages is 4 times/ton based on the same standard as the drawability below. It is indicated by the time until it occurs frequently.

Stretchability: Indicated by the number of thread breaks during stretching that occurred during stretching of polyethylene terephthalate filaments equivalent to 1 ton of polymer weight.

Emulsion stability of fiber treatment agent: After being adjusted to a water emulsion type fiber treatment agent at 50°C, the emulsion stability after being allowed to stand at room temperature for 3 days was evaluated based on the following criteria.

◎, very good ○: good X: adhesion that caused separation: i 500 D/2, number of first twists 40 T/
10cIR.

PKXUL is an untreated cord with a twist count of 40T/10cM (
The specimens were treated and heat set with a latex-based adhesive (trade name), C9 (trade name), and the pull-out adhesive strength to rubber was evaluated.

As is clear from the results in Table 1, the fiber treatment agent of the present invention (Examples 1 to 6) does not cause yarn breakage, smoke generation, or tar formation, and has excellent emulsion stability and adhesion of treated fibers to rubber. is also good.

On the other hand, when a commonly known compound is used as the smoothing agent compound fA+ (Comparative Example 1), when the emulsifier compound (E) is not used (Comparative Example 2), and when an emulsifier other than the present invention is used (Comparative Example 3). 4) causes smoke and tar formation and does not improve thread breakage.

Example 7 During the production of a 1260 denier, 204 filament polycaproamide yarn by a normal direct spinning and drawing method,
After spinning and before stretching, a conventional water-containing fiber treatment agent, which is an antistatic composition, was applied, and a 1.0% stretch was applied using a bleached stretch roll.

Next, a fiber treatment agent having the composition shown in Example 4 was applied by a loaner, and then stretched at 230° C. using a hot roller to obtain a drawn yarn with a maximum stretching ratio of 9.7 g/d. At this time, in the case of the fiber treatment agent of the present invention, the number of thread breakages was 1.1 indentations/ton during drawing of 1 ton of polycapramide, which showed good operability. On the other hand, when the fiber treatment agent used in Comparative Example 1 was used in place of the fiber treatment agent of the present invention, the number of thread breakages was a22 dents/ton, which was poor.

Examples 8 to 13 Using the fiber treatment agent having the composition shown in Table 2, Example 1
The results of experimental evaluation using the same method as in ~6 are also shown in Table 2.

As is clear from the results in Table 2, for fiber treatment agents,
(C) By containing an ethylene oxide adduct of an alkylamine, the effect of preventing smoke generation and tar formation becomes even more remarkable.

Patent applicant Higashi Shikikai Co., Ltd.

Claims (1)

[Claims] France) General formula RO (OCXC!0OYO) n0cXO
OZ (However, RO in the formula is a monohydric alcohol residue having 6 to 30 carbon atoms, -6cxco- is -0CA, SA,
GO-. 0CAs OA4 Co- and -ocAsco- (where A, , A, , A, and A4 have 1 to 6 carbon atoms)
, S is a sulfur atom, and A5 is an alkylene group with 1 to 1 carbon atoms.
-0YO- is a dicarboxylic acid residue selected from polyhydric alcohol residues, alkylene oxide adduct residues of polyhydric alcohols, and alkylene oxide adduct residues of polyhydric phenols. 2 represents -OR or -OR' (herein, -OR' represents a monohydric alcohol residue having 1 to 30 carbon atoms), and n represents an integer of 1 to 6. ]: at least one compound to be removed and (Bl fal a reaction product of a higher fatty acid, a polyhydric alcohol and a polyethylene oxide and/or a polypropylene oxide; and (b) a castor oil compound containing ethylene oxide and / or at least one emulsifier selected from propylene oxide adducts in a proportion of (Al/(Bl) of 40 to 80 parts by weight, 760 to 80 parts by weight)
A fiber processing agent containing 20 parts by weight (total 100 parts by weight).